Method for producing 1,2-dichloroethane and vinyl chloride from ethylene and hydrogen chloride and oxygen



United States Patent 3 504 043 METHOD FOR PRODUCING 1,2-DICHLOROETH- ANE AND VINYL CHLORIDE FROM ET HYLENE AND HYDROGEN CHLORIDE AND OXYGEN Naoya Kominami, Yoshiaki Yamasaki, Tokio Sakurai, and

Kusuo Kawarazaki, Tokyo, Japan, assignors to Asahi Kasei Kogyo Kabushiki Kaisha, Osaka, Japan, a corporation of Japan No Drawing. Filed Oct. 6, 1964, Ser. No. 401,985

Claims priority, application Japan, Oct. 7, 1963,

38/52,463; Oct. 8, 1963, 38/ 52,532; Apr. 8, 1964, 39/ 19,479

Int. Cl. C07c 21/02, 17/02, 17/10 US. Cl. 260-656 4 Claims This invention relates to a method for producing 1,2- dichloroethane and vinyl chloride from ethylene, hydrogen chloride and oxygen by gas phase catalytic reaction with a high yield.

As for methods producing 1,2-dichloroethane from ethylene, hydrogen chloride and oxygen, there have been known heretofore oxychlorination methods of ethylene. In these conventional oxychlorination methods of ethylene, a Deacon catalyst i.e., a catalyst consisting of a chloride such as cupric chloride or ferric chloride alone, or the same chloride added with an alkali metal salt or a salt of a metal of the lanthanide group has been used. However, the activity of these catalysts are low. If the reaction temperature is raised to increase conversion, side reactions become active, and the yield of 1,2-dichloroethane is exceedingly reduced. If a low temperature is used, side reactions can be retarded, but the contact time must be extended greatly. Otherwise it is impossible to obtain 1,2-dichloroethane with a high one pass yield. Moreover, methods using conventional catalysts have had drawbacks in construction material and the capacity of the reaction tower when they are put into practice in commercial plant.

An object of the present invention is, accordingly, to provide a method for producing 1,2-dichloroethane and vinyl chloride at a relatively short contact time at an exceedingly low reaction temperature and with a high one pass yield by use of a catalyst much more active than the conventional Deacon catalyst. Another object of the present invention is to provide a method which uses a catalyst possessing high activity even at a low temperature and accordingly affords a great advantage in the minimum requirement of the construction material of the reaction tower used in the reaction of corrosive hydrogen chloride. A still further object of the present invention is to provide a method which can increase the capacity of the reaction tower extremely by use of slightly higher temperature. A yet still further object of the present invention is to provide a method which produces 1,2-dichloroethane together with a considerable amount of vinyl chloride but which scarcely produces any other chlorides.

It has now been discovered that these and other objects may be accomplished by the method of the invention. According to the present invention, in the production of 1,2- dichloroethane and vinyl chloride by gas phase reaction, there is used an eificient and active catalyst supported on active carbon consisting of a combination of at least one member of the compound of the group consisting of chlo rides, oxides, hydroxides, fluorides, bromides, iodides, sulfides, sulfates, nitrates, cyanides of a metal of the group consisting of gold and platinum, platinum ammonium chlorides and hydrochlroplatinous acid; another member of the group consisting of metallic copper, copperchlorides, copper-oxides, copper-hydroxides and acetates, sulfides, formate, iodides, bromides, carbonates, chlorates, phosphates, sulfates and oxalates of copper; or a catalyst further combining the above-mentioned catalyst with at 3,504,043 Patented Mar. 31, 1970 least one promoter from the group consisting of chlorides, oxides, hydroxides, nitrates, sulfates, sulfides, carbonates, phosphates and acetates of a metal from the group consisting of silver, zinc, cadmium, chromium, mercury, lead, iron, ruthenium, palladium, osmium, iridium and rhodium, the above-mentioned oxides, hydroxides, nitrates, sulfates, sulfides, carbonates, phosphates and acetates of all metals of the kind readily convertible to chloridefThe reaction temperature is in the range of from C. to 300 C., preferably from C. to 200 C.

An important aspect in the practice of the present invention is the necessity of use of active carbon as a carrier. In the general catalytic reaction, substances such as silicagel, active carbon, active alumina, kieselguhr, silicon carbide, magnesium oxide or the like is used as a carrier. However when one of the above-mentioned common carriers other than active carbon is used, or when no carrier is used in the present catalyst system, the activity of the catalytic system is exceedingly low compared with the case in which active carbon is used as a carrier, though both 1,2-dichloroethane and vinyl chloride are formed slightly. Such a difference of activity is much larger than what is expected from the difference of surface area. It is believed that the function of the active carbon is not merely that of a carrier but that its functional groups have a favorable effect on the reaction. In other words the function of the present catalyst and that of the active carbon cooperate in producing 1,2-dichloroet-hane and Vinyl chloride with high activity and high yield. Commercially available active carbon which is not treated in any way, or treated with inorganic acid such as nitric acid, hydrochloric acid or the like can be used as carriers. The catalyst can be prepared preferably by the impregnation method.

The above-mentioned metal chlorides or metal compounds readily convertible to chloride by hydrogen chloride or by a mixture of hydrogen chloride and oxygen, e.g. such as the above-mentioned metals, metal oxides, metal hydroxides, nitrates, sulfates, sulfides, carbonates,

. phosphates or acetates supported on active carbon can be used as a catalytic system. The amount of catalyst used varies according to the combination. As for the ratio of catalyst such as gold or platinum compound to promotor, the range of from 1 to 100 mol of promotor vs. 1 mol of catalyst is preferable.

It is possible to produce 1,2-dichloroethane and vinyl chloride with excellent activity and high yield by use of a principal catalytic system consisting of at least one member of the group consisting of chlorides, and compounds readily convertible to chloride such as oxides, hydroxides and fluorides, bromides, iodides, sulfides, sulfates, nitrates, cyanides of a metal of the group consisting of gold and platinum, platinum ammonium chlorides and hydrochloroplatinous acid, a metal of the group consisting of gold and platinum; and another member of the group consisting of copper chlorides and substances readily convertible to chlorides, such as metallic copper, copper oxides, copper hydroxides, and acetates, sulfides, formate, iodides, bromides, carbonates, chlorates, phosphates, sulfates and oxalates of copper. However, by further adding a promotor from the group consisting of chlorides, oxides, hydroxides, nitrates, sulfates, sulfides, carbonates, phosphates and acetates of a metal of the group consisting of silver, lead, ruthenium, palladium, osmium, iridium and rhodium, and the metals themselves, it is possible not only to increase the activity, but also to suppress the formation of oxidation products, and various chlorides other than l,2-dichloroethane and vinyl chloride thereby to increase the yield of 1,2-dichloroethane and vinyl chloride. When at least one chloride or a substance readily convertible to a chloride such 3 4 as the oxide, hydroxide, nitrate, sulfide, carbonate, phos- EXAMPLE 1 t' of ar ttfi zzdasm ittira325112.533: an by to the abbve mentiohed catalytic system the activity is E and angle chlond; i fg g g/nulaa eltli activlecarbon aving a su ace area O m. gr. e resu ting cattar 9533x2153 3332s.? reassess 4; 4 16 41.; .1... rlngs. e p at1num c on e an cupric c on e were of m1 mo per g. 0 carrler. gaseous mlxture aving a In carrymg out the method of the 1nvent1on, 1t 1s necesm 01 ratio of ethylene hydrogen chloride oxygen and sary, as above-mentioned, to maintain the reaction temnitro 0 gen of 12.28.10.50 was mtroduced into the reperature m the range of from 80 to 300 when action tube at a space velocity of 1200 hr. and the i rgactlon tirfilperatuse ls z F g i g 'g g reaction temperature was maintained at 175 C. The zl e lz e {Ease 1P ethylene conversion was 51.3 percent and the 1,2-did 6 l f l i 3 i S1 g g g i chloroethane yield and the vinyl chloride yield were 79.0 1 if; Owe a percent and 13.5 percent respectively, As by-products firofiiicgd iy ihz si de rzct ic ihs arg i g j gg z and oxidation product and other chloride yields were obt'nd' tf2. d. '1. chlondes other than the ob ect1ve substances e.g. tr1- an e m amoun S O 6% an 49% respectwey chloroethane, dichloroethylene, ethyl chloride, trichloro- CONTROL 1 ethylene and the like. When the preferable range of from 100 C. to 200 C. is used, the above-mentioned Employing the same catalyst as in Example 1 with drawbacks can be sufiiciently prevented. In the abovevarious carriers such as silica gel, gamma-alumina, silimentioned temperature range, 1,2-dichloroethane is the con carbide and magnesium oxide instead of active carprincipal product but at the higher temperature side, the hon, the reaction was carried out in the same apparatus ratio of formed vinyl chloride to 1,2-dichloroethane is and under the same reaction conditions as in Example increased. 1. The results are tabulated as follows:

Surface Ethylene 1,2- Kinds of area couver- (lichloro- Vinyl carrier (mi/g.) sion ethane chloride Other Silica gel 550 12. 4 38. 6 45. 5 15. 1 Gamma alumina- 330 6. 7 30. 5 42. 9 24. 2 Silicon carbide 0. 6 1. 1 90. 2 6. 8 3. 0 Magnesium oxide 130 2. 1 45. 4 34. 5 20. 1

The reaction can be carried out either at atmospheric pressure or under a pressure as long as the gas phase is EXAMPLE 2 maintained at the reaction conditions. As for reaction method, a fixed bed method, a moving bed method, and Various catalysts were deposited upon purified granua fluidized bed method can be used. The yield of 1,2-dilated active carbon and used in the reaction. The total chloroethane together with vinyl chloride in the present molar quantity of catalyst was kept at 0.150 mol per invention is so high as to be almost quantitative due to 100 g. of carrier. A mixed gas having a mol ratio of the low reaction temperature, there is no scattering of ethylene, hydrogen chloride and air of 11:26:63 was the catalyst and the activity can be maintained almost introduced into the reaction tube at a space velocity of perpetually. 1200 hrr- The reaction temperature was maintained at In order that those skilled in the art may more fully 180 C. The ratio of the constituents in each case and understand the nature of the invention and the method the results of the reaction are tabulated as follows:

Oomposi- Ethylene 1,2- Kinds of tions of converdichloro- Vinyl catalysts catalyst sion ethane chloride Other Pt-Cu-Ru 1=4=2 91.3 91.5 3 5 5.0 Pt-CuAg 1=4=2 90. 5 94. 3 2. 3 2. 9 Pt-Ou-Fe 1=5=1 82.3 73. 0 23. 1 3. 9 Pt-Cu-Hg- 1:42 8 s 60.5 31.0 9.5 Pt-Cu-Or... 1:513 22 .5 43.2 43.3 3.5 Au-Cu-PL. 1:211 88. 4 96. 2 2. 2 1.6 Au-Cu-Cd- 1121 74. 7 84-. 1 13. 0 2. 9 Au-Ou-Zn- 1;2=2 7s. 3 s0. 4 14. 5 5. 19 .Au-Ou-Ir 1:2;1 90 1 97.0 1.4 1.6

of carrying it out, the following examples are given. EXAMPLE 3 Ethylene conversion, 1,2-di-chloroethane yield and vinyl chlorid yield a defined a foll w .Platinum nitrate and cupric sulfate were deposited upon granulated active carbon. The catalysts deposited upon Ethylene c i =WX 100 the active carbon were diluted by mixing with Raschig y mo 8 6 rings, filled in a reaction tube and used in the reaction.

The deposited platinum nitrate and cupric sulfate were Lzdmhloroethane y1 e1d 0.02l2mol and 0.242 mol respectively per 100 g. of active ll2 dlchloroethane 111015 producedx 100 carbon. A mixed gas having a mol ratio of ethylene, hy-

Ethylene mols reacted drogen chloride and air of 12:28:60 was introduced into Vinyl chloride yield: the reaction tube at a space yelocity of 1500 hI. The 1 M id 1 d d reaction temperature was var1ed as described hereinafter. w X 100 The reaction reached a stationary state in about one hour.

Ethylene mols reacted The results are tabulated as follows:

The reaction was carried out with the same apparatus and the same reaction conditions as in Example 3 at various temperatures except that 0.242 mol of cupric chloride alone was deposited upon 100 g. of granulated active carbon. Results were tabulated as follows:

Reaction temperature, Ethylene 1, 2-dichloro- Vinyl 0. conversion ethane chloride Other EXAMPLE 4 Auric chloride and cupric acetate were deposited upon from 50 to 100 mesh active carbon and filled in a reaction tube of 80 mm. diameter to carry out reaction in a fluidized bed.

The deposited auric chloride and cupric acetate were present in respective amounts of 0.0318 mol. and 0.0743 mol'per 100 g. of active carbon.

A gaseous mixture of ethylene, hydrogen chloride and air having a mol ratio of 12:28:60 was introduced from the bottom of the fluidized bed and a contact time of 1.5 seconds and a reaction temperature of 220 C. was maintained.

The reaction reached the stationary state in a short time. The ethylene conversion at that time was 47.2 percent, and the resultant 1,2-dichloroethane yield was 93.8 percent and the vinyl chloride yield was 4.3 percent. The sum of these two yields was 98.1 percent and the rest was almost entirely carbon dioxide.

What is claimed is:

1. A method for producing 1,2-dichloroethane and vinyl chloride comprising contacting a gaseous mixture of ethylene, hydrogen chloride and oxygen with a catalyst supported upon an active carbon carrier at a temperature of from 80 C. to 300 C., the said catalyst consisting of at least one member of the group consisting of gold chlorides, metallic gold, gold oxides, gold hydroxides, gold fluorides, gold bromides, gold iodides, gold cyanides, gold sulfides, gold sulfates, gold nitrates, platinum chlorides, platinum metal, platinum oxides, platinum hydroxides and hydrochloroplatinous acid, platinum ammonium chorides, platinum fluorides, platinum bromides, platinum iodides, platinum sulfates, platinum sulfides, and platinic nitrate; and at least one member selected from the group consisting of copper chlorides, metallic copper, copper oxides, copper hydroxides and copper acetates, copper sulfides, cuprous formate, cuprous iodide, cupric bromide, cupric carbonate, cupric chlorate, cupric phosphate, cupric sulfate and cupric oxalate.

2. A method for producing 1,2-dich1oroethane and vinyl chloride comprising contacting a gaseous mixture of ethylene hydrogen chloride and oxygen with a catalyst supported upon an active carbon carrier at a temperature of from C. to 300 C., the said catalyst consisting of at least one member of the group consisting of gold chlorides, gold metal, gold oxides, gold hydroxides, platinum chlorides, platinum metal, platinum oxides, platinum hydroxides and fluorides, bromides, iodides, sulfides, sulfates, nitrates, and cyanides of a metal selected from the group consisting of gold and platinum, platinum ammonium chlorides and hydrochloroplatinous acid and at least one second member selected from the group consisting of copper chlorides, metallic copper, copper oxides, copper hydroxides, and copper acetates, copper sulfides, cuprous formate, cuprous iodide, cupric bromide, cupric carbonate, cupric chlorate, cupric phosphate, cupric sulfate and cupric oxalate and at least one third member selected from the group consisting of silver, zinc, cadmium, mercury, lead, chromium, iron, ruthenium, palladium, osmium, iridium and rhodium and the chlorides, oxides, hydroxides, nitrates, sulfates, sulfites, carbonates, phosphates and acetates thereof. Consisting of silver, zinc, cadmium, mercury, lead, chromium, iron, ruthenium, palladium, osmium, iridium and rhodium, and their chlorides, oxides, hydroxides, nitrates, sulfates, sulfites, carbonates, phosphates, and acetates.

3. A method for producing 1,2-chloroethane and vinyl chloride comprising contacting a gaseous mixture of ethylene, hydrogen chloride and oxygen with a catalyst supported upon an active carbon carrier at a temperature of from 80 C. to 300 C., the said catalyst consisting of at least one member of the group consisting of gold, platinum and chlorides thereof and at least one member of the group consisting of copper and the chlorides thereof.

4. A method as claimed in claim 3, further comprising a promoter added to said catalyst selected from the group consisting of silver, zinc, cadmium, lead, chromium, iron, ruthenium, palladium, osmium, iridium and rhodium and the chlorides thereof.

References Cited UNITED STATES PATENTS 3,055,955 9/ 1962 Hodges 260656 2,308,489 l/l943 Cass 260656 2,838,577 6/1958 Cook et al. 260656 3,291,846 12/1966 Otsuka et al 260656 3,354,234 11/1967 Hayden et al. 260656 FOREIGN PATENTS 1,143,807 2/ 1963 Germany.

968,933 9/1964 Great Britain.

LEON ZITVER, Primary Examiner H. T. MARS, Assistant Examiner US. Cl. X.R. 

1. A METHOD FOR PRODUCING 1,2-DICHLOROETHANE AND VINYL CHLORIDE COMPRISING CONTACTING A GASEOUS MIXTURE OF ETHYLENE HYDROGEN CHLORIDE AND OXYGEN WITH A CATALYST SUPPORTED UPON AN ACTIVE CARBON CARRIER AT A TEMPERATURE OF FROM 80*C. TO 300*C., THE SAID CATALYST CONSISTING OF AT LEAST ONE MEMBER OF THE GROUP CONSISTING OF GOLD CHLORIDES, METALLIC GOLD, GOLD OXIDES, GOLD HYDROXIDES, GOLD FLUORIDES, GOLD BROMIDE, GOLD IODIDES, GOLD CYANIDES, GOLD SULFIDES, GOLD SULFATES, GOLD NITRATES, PLATINUM CHLORIDES, PLATINUM METAL, PLATINUM OXIDES, PLATINUM HYDROXIDES AND HYDROCHLOROPLATINOUS ACID, PLATINUM AMMONIUM CHORIDES, PLATINUM FLUORIDES, PLATINUM BROMIDES, PLATINUM IODIDES, PLATINUM SULFATES, PLATINUM SULFIDES, AND PLATINIC NITRATE; AND AT LEAST ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF COPPER CHLORIDES, METALLIC COPPER, COPPER OXIDES, COPPER HYDROXIDES AND COPPER ACETATES, COPPER SULFIDES, CUPROUS FORMATE, CUPROUS IODIDE, CUPRIC BROMIDE, CUPRIC CARBONATE, CUPRIC CHLORATE, CUPRIC PHOSPHATE, CUPRIC SULFATE AND CUPRIC OXALATE. 